Treating of nonferrous materials



Patented Feb. 6, 1945 TREATING F NONFERROUS MATERIALS.

Louis S. Deitz, Jr., Westfield, N.. J., assignor to Nassau smelting &. Refining Company, Incorporated, New York, N. Y., a corporation ollNew York No Application December 14, 1943,

' Serial No. 514,275

20 Claims. (Cl. 75-24) This invention relates to the treating of nonferrous materials and more particularly to the production of copper base products containing substantial quantities of tin by treating nonferrous materials and secondary metals.

' It has been customary to treat materials containing copper and one or more of the metals tin, lead and zinc to utilize the metal values therein in the production of ingots of predetermined compositions. Relatively impure materials of this nature are smelted in a blast furnace to produce blast furnace pigs that are treated subsequently scrap brass and briquettes of zinc spelter, is included as part of the charge and tin-oxide material, such as high tin drosses and tin ores, are

also incorporated in the charge, the zinc-bearing material being present in sufllcient quantity to reduce a substantial portion of-the tin oxide to metallic tin.

This process is based on the observation that -when metallic zinc and tin'oxide are heated to a temperature above the melting point of copper, th zinc reduces the tin oxide to metallic tin and the reaction proceeds exothermically. This indlin a reverberatory or other furnace to refine them further. Such blast furnace pigs generally contain only a small amount of tin, seldom as much as and when they are used in reverberatory charges to make alloys containing substantial quantities of tin virgin tin is added to the charges to increase the tin contents of the finished alloys.

It las been the practice to make in a rever beratory furnace products such as those consisting of 85% 01' copper, 5% of tin, 5% of lead and 5% of zinc, or 80% of copper, of tin and 10% of lead, or 88% of copper, 8% oi tin and 4% of zinc, respectively. The charges fed into the reverberatory furnace usually included such materials as blast furnace pigs, copper and bronze wire, brass and bronze turnings, metallic copper,

tin and zinc, slags from previous charges, and

the usual slagging and reducingmaterials;

The composite analyses or. the metal 'values of these materials, other than the metallic tin, are

such that the products obtained therefrom would contain insufllcient tin to produce high tin ingots if virgin tin were not added to the charge. However, the supply of virgin tin is limited and its useis restricted. Consequently, when non-ferrous alloys containing tin are produced, it is desirable to employ processes in which some of the required tin may be supplied from other sources.

Thus, there is need for processes in which the tin content of blast furnace pigs and of reverberatory or other types of ingots canbe increased without the use of metallic tin.

It is an object of this invention to provide new and useful processes for treating non-ferrous materials.

In accordance with one embodiment of the invention, a suitable furnace is charged with materials containing copper and other non-ferrous metals, together with the usual slagging and reducing materials, andthe materials are heated to a temperature high enough to cause the opera- 7 tion to proceed. Zinc-bearing material, such as.

cated that zine could be used as an active reducing agent for tin oxide in metallurgical processes.

such as in blast furnace smelting operations and reverberatory refining processes, because the heat of reaction tends to accelerate the reaction:

From this observation it was conjectured that,

if a mixture 01 tin oxide and brass, or other alloy or mixture of copper. and zinc (with or without the presence of other materials, such as lead), is heated to a temperature above the melting point of copper, the'zinc should reduce the tin oxide to metallic tin, and that the tin would alloy with the copper. Under normal operations of this nature in accordance with this invention, where tin oxide is present in the charge, a reducing agent, such as coke, is always-added to the charge and this reducing agent will reduce a considerable portion of the tin and other metal oxides in the charge. In accordance with thisinvention, the zinc present should be suilicient to, insure substantially complete reduction 01' any tinoxide not otherwise reduced. Experiments have demonstrated that this process may be used with extremely satisfactory results ,on a commercial scale in commercial furnaces, and that it provides an economical and readily controlled means of producing copper base alloys having high tin contents.

Such a process has the advantage that the metallic tin produced is taken up by the copper and is not volatilized. Only a relatively small amount of tin is collected in flue dusts and the slag contains very little tin. Consequently, tinoxide materials containing high percentages 01' tin may be used to build-up the tin content of the resulting productwithout excessive loss of tin. and this process permits the use or high tin drosses and ores which formerly were not treated in blast furnaces and reverberatory furnaces used to make copper base materials. Thus, products having high tin contents may be made without the use or metallic tin. v

The above-described and other objects and features of the invention will be apparent from the followingdescription of specific examples of processes'embodying the invention, in which tin ore is used to supply a portion of the tin required contents, to reverberatory furnace charges of this accepts nature, because it wouldbe anticipated that an excessive amount of :the "tin would go oi! as slag and as fume, which would be collected in the flue dusts. It also would be anticipated that to make tin-containing copper base alloys in a 5 the normal reverberatory furnace charges conreverberatory furnace. tain insuillcient reducing material to reduce these Example I high tin-oxide materials to metallic tin.

I In accordance with the processes embodying In accordance with this embodiment of the this invention, the reverberatory charge is so adinvention, "the process was performed inv such 1 justedthat thereis suflicient zinc therein to inmanner as to make ingots con g approxisure the substantially complete reduction of all mately 88% of copper, 6% of tin, 1.5% of lead of the tin oxide present in the charge, including and the balance zinc. This was accomplished by that found in the tin ore; The nascent zinc feeding into a reverberatoryfurnace charges convapors produced in the charge permeate the taining various scrap materials, such asbrass and i5 charge and effectively reduce the tin oxide not bronze turnings, reclaimed wire, metallic zinc, I otherwise reduced to metallic tin, which immeditin-containing cable sheaths,.and tin oxide ore, ately combines with the molten copper produced together with the usual reducing and s'lagging' to form a copper-base alloy containing tin. materials, such as coke, sand and soda ash, and If it is desired to produce ingots containing heating the charge. more than about 6% of tin, this can be accom- A typical run of this nature was carried out plished by adding to the reverberatory furnace with the use of a charge containing the followcharges larger quantities of tin ores and making ingmaterials: a r certain that the zinc content of the charge is sufllciently high to insure substantially complete 7 Approximate composition reduction of the tin oxide contained in, the ore. Pound r It is also possible to use iron-free tin drosses condad Material taining upward of 40% of tin oxide instead of a? 3? a the tin ore, if desired. By the use of greater quantities of high tin oxide materials, ingots cona taining from 8% to 10% tin may be produced. 22% fi23522 3 3. 1: 9: is If a lead-free alloy is to be made, the charge is %;23: fig fi 2!} 6 L 5 g made up of materials that contain little, if any, ne sma s 2-" .5 21411 Miscell a neoim grad 5511155 84 4 2 2 Example H 1 4 Z 5 35 In accordance with this embodiment of the in- 5,660 nl l g a 'gr' fiipsliifi' a5 a 2 2 vention, a charge oge the following compositiog was fed into a rever ratory furnace and treats 81 55:? Wmmgs s 3 (68 Ni? in a manner similar to that described in Ex- 5,680 Beverberatoryim'nacescrap. 87 7 2.5 Bal ample I: f 2,064 Bolivian tin c0ncentrates- 66 38 r that! zinc mo 99 1 '105 3% tin-lead cable sheath a 97 'Aplmimm adder l Mama] Per Per Per Per Approximately 1,200 pounds of coke, 550 pounds cent cent cent cent of sand and 1,700 pounds of soda ash were also Cu 311 Pb Zn employed as reducing and slagging ingredients. The tin ore was mixed with about 300 pounds 'fi'ggg gmgggwg Pigs of lime and 100 pounds of line charcoal to'pro- 91000 90-15 brass mmin'III duee a pasty mass which could be readily han- ,gf gg fi vgleriirlndhto 6153;? volatilization of the tin. If 2 g2copper es t e tin 0 de ore may be briquetted with fore it is introduced into the furnace. 2 $23 .gg gggg ggg'g The special blast furnace pigs contained about '200 3% tin-lead. cablb a 01 8% or more of tin. while the Bolivian tin con- 5 'centrates contained 66% of tin. The ingots pro- About 500 pounds of charcoal, 800 pounds of fluted l d n ver f 88.9% of c pp coke, 650 pounds of sand and 1,500- pounds of 5.6% Of tin and 1.5% .Of 188411711211 the balancesoda, ash were also added, ['he tin ore conbeine zinctained 66% of tin and was mixed with lime and About 20% of the tin required to make the charcoal, as in the previous example, before it alloy of this composition came from the tin ore was introduced into the furnace. The special included in the charge, and about 40% was deblast furnace pigs contained about 8% of tin. rived from the special blast furnace pigs, while 7, The ingots produced contained 88.01% of copthe rest was provided by the tin contents of the per, 5.81% of tin, and 1.54% of lead, with the scrap metals treatedand the 560 pounds of pig 5 balance being zinc. Almost 50% of the tin in tin added to the charge. .Thereducing and slag- I the ingots was supplied by the special blast furging reagents, such as coke, charcoal, send, lime, nace pigs, while about 10% of the tin came from soda ash, and the like, employed. and the the tin ore. The remainder of the tin .-in the amounts thereof; were not substantially different ingots was provided by the tin contents of the than are used in the usual reverberatory iurnace, 7o scrap metals treated and by the tin residues 7 processesinwhich-notinoreisadded. which supplied slightly more than 25% of the Heretofore, it had not been considered comtin. Itwill be observed that no pig tin was added mercially feasible to add substantial quantities to this charge and that the entire tin content of of materials, such as ores, having. high tin oxide the ingots was obtained from secondary sources tsan'dfromtinore. 1 V

By utilizing these high tin oxide containing materials in blast furnace charges containing the requisite amount of zinc, blast furnace pigs containing 10% or more of tin can :be obtained; With theusual blast furnace charge, in which the materials employed contain relatively small quantities of tin, the pigs produced contain from about 2% to not over 5% of tin.

Thus, this invention contemplates generally the utilization of high tin oxide materials innon ferrous metal refining processes in which such materials had not formerly been used,- coupled with the inclusion in the furnace charges of zincbearing material in suflicient quantities to cause substantially all of the otherwise unreducedtin oxide in the tin-containing materials to be sub- I I 3 rials which comprises introducing into a furnace a charge including iiuxing material, carbonaceous redncin'gmaterial and material containing copper, zinc and'tin, and heating the charge to recover the metallic values therein, at least a sub stantial part oi the tin-containing material being one having a high tin oxide content and the amount of zinc-containing material present being sufllcient to insure the reduction to metallic tin of a substantial quantity of tin-containing material which otherwise would rem-ain'unreduced.

3. The process of treating non-ferrous materials which comprises introducing into a furnace a charge including limiting and reducing materials and material containing copper, zinc and a tin, and heating the charge to recover the metalstantially completely reduced thereby. The invention further contemplates the use of high tin oxide materials in a blast furnaceto produce high tin blast furnace pigs, followed by the utilization of such pigs in reverberatory furnace charges which also contain high tin oxide materials to produce ingots having the desired tin content, without the introduction of more than a relatively small amount of pig tin to the reverberatory furnace charge,

It has been difllcult to utilize certain tin ores, I

cry of the tin values therein, and without having to mix them with other higher grade ores.

Obviously, this invention is not limited to the use of the specific ores recited in the examples given ,hereinabove, but the prccesses embodying The processes embodying a charge including fluxing and reducing matethe invention may be practiced with satisfactory results by using other tin-bearing materials containing substantial percentages oftin oxide, By carrying out the processes in such manner that the furnace charges always contain enough zinc to insure the reduction of the tin oxide in the tin-bearing materials employed, a commercially complete reduction of .the tin oxide is obtained and the losses of tin in the slag and the amount of tin appearing as a constituent of the flue dust are sufiiciently low to make the process commercially feasible.

What is claimed is? l. The .process of treating non-ferrous materials which comprises'introducing in o a furnace a charge including fiuxing and reducing materials-and material containing copper,- zinc'and lic values therein, at least a substantial part of the tin-containing material being a tin ore having a high tin oxide content and the amount of zinc-containing material present being sui'ilcient to insurethe reduction to smetallic tin oi! a substantial quantity of tin oxide.

4. The process of treatin non-ferrous materials which comprises introducing into a furnace a charge including fluxing and reducing materials and material containing copper, zinc and tin, and heating the charge to recover-the metallic values therein, at least a substantial part-oi the tincontaining material being an iron-free tin dross having a high tin oxide content and the amount of zinc-containing material present being suflic ent to insure the reduction to metallic tin of a substantial quantity of tin oxide.

-5. The process oi! treating non-ferrous materials which comprises introducing into a furnace a charge including fluxing and reducing materials and material containing coppenzinc and tin, and heating the charge to recover the metallic values therein, at .least a substantial part of the tin-containing material being one having a tin oxide content of upward of 40% and the amount of zinc-containing material present be- .ing sufilclent to insure the reduction to metallic tin of a substantial quantity of tin oxide.

6. The process of treating non-ferrous materials which comprises introducing into a furnace rials and material containing copper, zinc and tin, and heating the charge'to recover the metal lic values therein, at least a substantial part or the tin-containing material being a tin oxide ore containing at least 60% of tin and the amount of zinc-containing material present being sumcient-to insure the reduction to metallic tin of V taining copper, zinc and tin,. and heating the charge to recover the metallic values therein, at k a least a substantial part of the tin-containingmaterial being one having a high tin oxide contentand the amount of zinc-containing material present being sumcient to insure the reduction to metallic tin of a substantial quantity of tin oxide.

tin, and heating the charge to recover the metallic values therein, at least a substantial part of the tin-containing material being one havingahigh tin oxide content and the'amount of 'zinccontaining material present being suflicient t'o insure the reduction to metallic tin of asubstantial quantity of tin oxide.

2. The process of treating non-ferrous mate- 1 8. The process of treating non-ferrous mate rials. which comprises introducing into a furnace a' charge including copper-bearing and other ma-' terialscontaining non-ferrous metals in such 1 proportions as to produce an ingot metal consisting principally-of copper, including in the charge a cufhcient'qriantity of high tin oxide material to materially increase'the tin content of the ingot metal and sumcient zinc-bearing material to insure the reduction to metallic tin of a substantial quantity of tin oxide which would be unreduced, and heating the charge, whereby the nascent zinc produced assists in the reduction of the tin oxide material.

9. Theprocess of treating non-ferrous materials which comprises feeding into a reverbera-- tory furnace a charge including copper-bearing and other materials containing metal of the group consisting of lead, zinc and tin in such proportions as to produce an ingot metal consisting of upward of 70% of copper, including in the charge a substantial quantity of zinc-bearing material and material containing upward of 40% of tin oxide, and heating the charge, the nascent zinc derived from the zinc-bearing material assisting in the reduction of a substantial quantity of the tin oxide in the tin oxide material.

0. The process of producing tin-containing ingots without the use of substantial quantities of metallic tin, which comprises smelting in a blast furnace a charge including copper, zinc and tin-bearing materials in which a substantial part of the tin-bearing material is one having a high tin-oxide content and in which sufiicient zinc-containing material is present to insure the reduction of a substantial quantity of the tin oxide in the charge to metallic tin, whereby a high tin blast furnace metal is produced, introducing such blast furnace metal into a rever-. beratory furnace together with material conthe tin-bearing material is one. having a high "tin oxide content and in which suflicient zinccontaining material is present to insure the reduction of a substantial quantity of the tin oxide in the charge to metallic tin, whereby a high tin blast furnace metal is produced, introducing such blast furnace metal into a reverberatory furnace together with material containing copper, zinc and tin, including in the reverberatory furnace charge a substantial quantity of tin oxide ore and zinc-containing material in sumcient quantity to insure the reduction to metallic tin of a substantial amount of thetin oxide in the charge, and heating the latter charge.

12. The process of producing tin-containing ingots, which comprises smelting in a blast furnace a charge including copper, zinc and tinbearing materials, in which a substantial part of the tin-bearing material is one having a high tin oxide content and in which sufllcient zinc-containing material is present to insure the reduc-' tion of a substantial quantity of the tin oxide to metallic tin, whereby a high tin blast furnace' metal is produced, introducing such blast furnace metal into a. reverberatory furnace together with material containing copper, zinc and tin, including in the reverberatory furnace charge a substantial quantity of tin oxide ore having a tin content ofu-pward of 60% and zinc-containing material in suflicient quantity to insure the reduction of a substantial amount of the tin oxide in the tin oxide material, and heating the latter charge. a

13. The process of producing tin-containing ingots without the use of metallic tin, which com- 5 prises smelting in a blast furnace a charge in:

cluding copper, zinc and tin-bearing materials, in which a substantial part of the tin-bearing ma- .terial is one having a tin content of upward of f 40% and in which suflicient zinc-containing ma- 1 terial' is present to insure the reduction of a substantial quantity of the tinoxide to metallic tin,

whereby a high tin blast furnace metal is pro-- duced, introducing such blast furnace metal into a reverberatory furnace together with :material containing copper, zinc, and tin, including in the reverberatory furnace, charge a tin oxide ore having a 'tin content of upward of 60%, also including in the reverberatory furnace charge zinccontaining material in sumcient quantity to in? lsure the reduction to metallic tin of a substantial tallic tin, which comprises smelting in a blast furnace a charge including copper, zinc and tinbearing materials, including inthe blast furnace charge a suflicient quantity of tin-bearing material having a tin content of upward of 40% to produce a blast furnace metal having a tin content of upward of 5%, also including in the blast furnace charge sufficient zinc-containing material to reduce to metallic tin a substantial quantity of tin oxide which otherwise would be unreduced, introducing such blast furnace metal into a reverberatory furnace together with material contalning copper, zinc and'tin, including in the reverberatory furnace charge a tin oxide ore 40 having atin content of upward of 60%, also including in the reverberatory furnace charge zinccontaining material in sumcient quantity-toreduce to metallic tin a substantial quantity of .tin

oxide which otherwise would be unreduced, and I heating the reverberatory furnace charge to a temperature sufllciently high and for a period sufiiciently long to recover the metallic values in the charge.

15. The process of treating non-ferrous mate- 5 rials, which comprises introducing into a furnace 25 ingots with the use of a minimum amount of mea charge including carbonaceous reducing material and material containing copper, zinc and tin, and heating the charge to recover the metallic values therein, at least a substantial part of the tin-containing material in the charge being one having a high tin oxide content and the amount of zinc-containing material present in the charge being sufficient-to insure substantially complete reduction to metallic tin of the otherwise unreduced tin oxide in the ,charge.

35 taining non-ferrous metals in such proportions as to produce a metal consisting principally of copper, including in the charge a sufllcient quantity of high tin oxide material to materially increase the tin content of the metal produced and 7 suflicient zinc-bearing material to insure the reduction to metallic tin of substantially all tinbearing material in the charge which otherwise would be unreduced, and heating the charge.

17. The process of treating-non-ferrous mate- 76 rials, which comprises introducing into a furnace a charge including carbonaceous reducing material and material containing copper, zinc and tin in such proportions as to produce a copper base metal containing more than of tin,'and heating the .charge to recover the metallic values therein, at least a substantial part of the tincontainin material in the charge having a tin oxide content of upward of 40% and the amount of zinc-containing material present in the charge being sufllcient to insure the substantially complete reduction to metallic tin of the otherwise unreduced tin oxide in the charge.

18. The process 0.5 treating non-ferrous materials, which comprises feeding into a; furnace a charge including carbonaceous reducing material and copper-bearing and other materials containing metals of the group consisting of lead, zinc and tin in such proportions as to produce a metal consisting of upward of 70% of copper and more than 5% of tin, including in the charge a substantial quantity oi zinc-bearing material and tin oxide material containing upward of 50% of tin oxide, and heating the charge, the nascent zinc derived from the zinc-bearing material eifecting the reduction of a substantial quantity or the tin oxide in the charge which otherwise would be unreduced. i

19. The process of treating non-ferrous material, which comprises introducing into a rever-' beratory furnace a charge including carbonaceous reducing material and material containing copper, zinc and tin, and heating the charge to recover the metallic value therein, a substantial part or the tin-containing material in the charge being a tin ore having a high tin oxide contentand the amount of zinc-containing material present in the charge being'sufllcient to insuresubstantially complete reduction to. metallic tin 01 the otherwise unreduced tinoxlde in' the charge.

20. The process of producingtin-containing ingots, which comprises smelting in a blast furnace a charge including carbonaceous reducin material and copper, zinc and tin-bearing materials in such proportions as to produce a blast Y furnace metal consisting principally of copper and containing in excess or 5% of tin, in which charge p a substantial part or the tin-bearing materials has a high tin oxide'conteni; and'the amount of zinc-containing material is sumcient to insure substantially complete reduction to metallic tin of the otherwise unreduced tin oxide in the charge, introducing such blast furnace metal into a reverberatory furnace as part of a charge in- 

